Triazolyl phosphorus compounds

ABSTRACT

Triazolylorganophosphorous derivatives of the formula   WHEREIN X represents fluorine, chlorine or bromine, Z represents oxygen or sulphur, R1 represents alkyl, cycloalkyl, unsubstituted or substituted aryl or aralkyl, R2 represents alkoxy, alkylthio, amino, mono- or dialkylamino and R3 represents alkyl, alkoxy, alkylthio, phenyl, phenoxy, amino, mono- or dialkylamino, a process for their manufacture and their use in pest control.

United States Patent 1191 Dawes et al.

[ TRIAZOLYL PHOSPHORUS COMPOUNDS [75] Inventors: Dag Dawes, Pratteln; Beat Btihner,

Binningen, both of Switzerland [73] Assignee: Ciba-Giegy Corporation, Ardsley,

221 Filed: Nov. 29, 1972 21 Appl. No.: 310,530

[30] Foreign Application Priority Data OTHER PUBLICATIONS Chemical Abstracts, Vol. 7l, 1969, Item l0l86l(c) page 365, abstracting South African Patent No. 68/03,47l, 31 Oct. 1968.

14 1 Feb. 18, 1975 Primary Examiner-Henry R. .liles Assistant Examiner-Robert T. Bond Attorney, Agent, or Firml-larry Falber; Frederick H. Rabin; Philip P. Berestecki [57] ABSTRACT Triazolylorganophosphorous derivatives of the formula wherein X represents fluorine, chlorine or bromine, Z represents oxygen or sulphur, R represents alkyl, cycloalkyl, unsubstituted or substituted aryl or aralkyl, R represents alkoxy, alkylthio, amino, monoor dialkylamino and R represents alkyl, alkoxy, alkylthio, phenyl, phenoxy, amino, monoor dialkylamino, a process for their manufacture and their use in pest control.

7 Claims, No Drawings TRIAZOLYL PHOSPHORUS COMPOUNDS The present invention relates to triazolylorganophosphnrus derivatives, a process for their manufacture and their use in pest control.

The compounds have the formula wherein X represents fluorine, chlorine or bromine, Z represents oxygen or sulphur, R represents alkyl, cycloalkyl, unsubstituted or substituted aryl or aralkyl, R represents alkoxy, alkylthio, amino, monoor dialkylamino and R represents alkyl, alkoxy, alkylthio, phenyl, phcnoxy, amino, monoor dialkylamino Thc alkyl, alkoxy and alkylthio groups represented by R to R contain in the chain 1 to 19, preferably 1 to 6, carbon atoms and may be straight-chain or branched. unsubstituted or optionally substituted by halogen atoms, such as fluorine, chlorine, bromine and- /or iodine.

Examples of such groups include methyl, methoxy, methylthio, ethyl, ethoxy, ethylthio, 2-chloroethyl, propyl. 3,3.3trichloropropyl, propoxy, propylthio, isopropyl, n-. 1-, sec. and tert.butyl, 4-chloro-(n)-butyl, npentyl, n-dodecyl, (n)-nonadecyl.

The cycloalkyl groups represented by R, contain 3 to 8, but preferably 5 to 6, ring carbon atoms. Examples of such groups are cyclopentyl and cyclohexyl.

The aralkyl radical represented by R, is preferably a benzyl, phenethyl or diphenylmethyl group or is a group of the formula It (II) 2)&

2)b P 'l-aal Hal The aralkyl. in particular the benzyl and aryl. cspccially phenyl. groups may be unsubstituted or suhsti tuted Possible substitutents at these groups are prefcrabl fluorine, chlorine and/or bromine, alkyl and halogenoalkyl each with l to 6 carbon atoms, in particular CF alkoxy, alkylsulphinyl. and alkylsulphonyl. each with l to 6 carbon atoms. and/or nitro groups.

Preferred compounds on account of their action are those of the formula I, wherein X represents chlorine or bromine, Z represents oxygen or sulphur, R reprcsents alkyl with l to 19 carbon atoms, cyclopentyl, phenyl or benzyl which is unsubstituted or monoor polysubstituted by fluorine, chlorine, bromine, methyl, trifluoromethyl, methoxy, methylthio, ethoxy and/or nitro, phenethyl, diphenylmethyl or R represents methoxy, ethoxy, propoxy, 2- chloroethoxy, propylthio, methylamino, dimethylamino or isopropylamino, and R represents methyl, ethyl, methoxy, methylthio, ethoxy, ethylthio, propxy, 2-chloroethoxy, propylthio, phenyl, phenoxy, amino, methylamino or dimethylamino.

Particular repreferred compounds, however, are those of the formula I, wherein X represents chlorine, Z represents sulphur, R represents alkyl with l to 6 carbon atoms, cyclopentyl, phenyl, 3-trifluoromethylphenyl, benzyl, diphenylmethyl or N-- N-it sol NJ-x (III) acid binding acid binding HO-L H/JX agent:

N-- N-R -Co ntinued In the formulae II to VIII, the symbols R to R, X and Z, have the meanings given for the formula I, Hal represents fluorine, chlorine, bromine, or iodine, but in particular chlorine or bromine, R represents alkoxy, eth ylthio or phenoxy, and Me represents a monovalent metal, preferably an alkali metal, in particular sodium or potassium.

In the formulae II to Vlll, the symbols R to R, X and Z have the meanings given for the formula I, Hal repre sents fluorine, chlorine, bromine or iodine, but in particular chlorine or bromine, R represents alkoxy, ethylthio or phenoxy, and Me represents a monovalent metal, preferably an alkali metal, in particular sodium or potassium.

The following bases, for example, are suitable as acid binding agents, tertiary amines, such as triethylamine, dimethylaniline, pyridine, inorganic bases, such as hydroxides and carbonates of alkali and alkaline earth metals, preferably sodium and potassium hydroxide.

The reaction may be carried out preferably in solvents or diluents which are inert towards the reactants or in an excess ol a tertiary amine, e.g. pyridine. Suitable inert solvents or diluents are, for example, the following: aromatic hydrocarbons, such as benzene, toluene, henzines, halogenated hydrocarbons, chlorobenzone. polychlorobenzenes, bromobenzene, chlorinated alkanes with l to 3 carbon atoms, ethers, such as dioxan, tetrahydrofuran; esters, such as ethyl acetate; ketones, such as methyl ethyl ketone, diethyl ketone, nitriles etc.

The starting materials of the formulae III to IV are new and can be manufactured, for example, by halogenation or transhalogenation of 3-hydroxy-triazole derivatives which are unsubstituted in the 5-position, or esters thereof.

The compounds of the formula I display a broad biocidal activity and are thereofre suitable for combating various plant and animal pests.

In particular, the compounds of the formula I possess insecticidal and acaricidal properties and may be used against all development stages, e.g. eggs, larvae, pupae, nymphs and adults, of insects and representatives of the order Acarina. for example against insects of the families:

acid binding agent I R Me Tetranychidae and Dermanyssidae.

The insecticidal and/or acaricidal action can be substantially broadened and adapted to suit the particular circumstances by the addition of other insecticides and/or acaricides.

Suitable additives include, for example, the following active substances:

Bis- 0,0-diethylphosphoric acid anhydride (TEPP) Dimethyl-(2,2,2-trichloro-l-hydroxyethyl)- phosphonate (TRICHLORFON) l ,Z-dibromo-2,2-dichloroethyldimethylphosphate (NALED) 2,2-dichlorovinyldimcthylphosphate VOS) 2-methoxycarbamyl l -methylvinyldimethylphosphate (MEVINPHOS) i Dimethyl-l-methyl-2-(methylcarbamoyl)- vinylphosphate cis (MONOCROTOPHOS) 3 (dimethoxyphosphinyloxy)-N,N-dimethyI-ciscrotonamide (DICROTOPHOS) Z-chloro-Z-diethylcarbamoyl-l-methylvinyltlimethylphosphate (PHOSPHAMIDON) 0,0-diethylO(or S)-2-(ethylthio)-ethylthiophosphate (DEMETON) S-ethylthioethyl-0,0-dimethyl-dithiophosphate (THl- OMETON) 0,0-diethyl-S-ethylmercaptomethyldithiophosphate (PHORATE) 0,0-diethyl-S 2-ethylthio)ethyldithiophosphate (Dl- SULFOTON) 0,0-dimethyl-S-2-(ethylsulphinyl)ethylthiophosphate (OXYDEMETONMETHYL) 0,0-dimethyl-S-( l,2-dicarbethoxyethyldithiophosphate (MALATHION) 0,0,0,0-tetraethyl-S,S'-methylene-bisdithiophosphate (ETHION) O-ethyI-S,S-dipropyldithiophosphate 0,0-dimethyl-S-(Nmethyl-N- formylcarbamoylmethyl)-dithiophosphate MOTHION) 0,0-dimethyl-S-(N-mcthylcarbamoylmethylJdithio phosphate DIMETHOATE) (DICHLOR- (FOR- (),()-tlimethyl-O-p-nitrophenylthiophosphate (PA- RATHlON-METHYL) (),()-diethyl-O-p-nitrophcnylthiophosphate (PAR/ v THION) O-ethyl-O-p-nitrophenylphenylthiophosphate (EPN) 0,0dimethyl-O-(4-nitro-m-tolyl)thiophosphate (FENITROTHION) 0,0-dimethyl-O2,4,5-trichlorophenylthiophosphate (RONNEL) O-ethyl-O,2,4,5-trichlorophenylethylthiophosphate (TRICHLORONATE) 0,0-dimethyl-O-2,5-dichloro-4-bromophenylthiophosphate (BROMOPHOS) 0,0-dimethyl-O-(2,5-dichloro-4-jodphenyl)- thiophosphate (.lODOFENPl-IOS) 4-tert. butyI-Z-chlorophenyl-N-methyl-O- methylamidophosphate (CRUFOMATE) 1 l l,4,5,6,7,8,8-heptachloro,3a,4,7,7a-tetrahydro-4,7-

methylenindane [HEPTACHLOR] 1 ,2,3,4,l0,10-hexachloro-l,4,4a,5,8,8a-hexahydroendo-l ,4-exo-5 ,8-dimethanonaphthalene [AL- DRIN] l,2,3,4,10,lO-hexachloro-6,7-epoxyl,4,4a,5,6,7,8,8a-oxtahydro-exol ,4-endo-5,8- dimethanonaphthalene [DIFLORIN] l ,2,3,4,10,l-hexachloro-5,7-epoxyl,4,4 01,5,6,7,8,8a-octy-hydro-endo-endo-S ,8- dimethanonaphthalene [ENDRIN] The active substances of the formula I are also suitable for combating representatives of the division Thallophyta, e.g. viruses, bacteria and fungi. They thus possess fungicidal properties against phytophathogenic fungi on various cultivated plants, such as cereals, maize, rice, vegetables, ornamental plants, fruit trees, vines, farm products, etc.

With the new active substances it is possible to control or destroy fungi occurring on fruit, blossom, leaves, stems, tubers and roots, and from which parts of plants which grow later then also remain free. The active substances of the formula I are active in particular against phytopahtogenic fungi belonging to the following classes:

Oomycetes, Zygomycetes, Ascomycetes, Basidiomycetes, Denteromycetes.

In addition, the new active substances can also be used for treating seeds, fruit, tubers etc., and the protccting them from fungus infections, for example from smut fungi of all kinds, such as Ustilaginales, e.g. Ustilago, Tillctia, Urocystis, Turbicinia and Phoma types.

in addition to the above cited acaricides and insecticides, it is also possible to admix the active substances of the formula I with, for example, bactericides, fungistatic agents, baceteriostatic agents, nematocides and- /or e.g. the following fungicides, in order to broaden the activity spectrum:

dodecylquanidine acetate (DODINE) pentachloronitrobenzene (QUINTOZENE) pentachlorophenol (PCP) 2-( l-methyl-n-propyl)-4,6-dinitrophenyl-Z-methylcrotonate (BINAPACRYL) 2-( l-methyl-n-heptyl)-4,6-dinitrophenylcrotonate (DlNOCAP) 2,6-dichloro-4-nitroaniline (DICHLORAN) 2,3,5,-tetrachloro-benzoquinone (1,4) (CHLOR- ANlL) 2,3-dichloro-naphthoquinone (1,4) (DlCHLONE) N-(trichloromethylthio) phthalimide (FOLPET) N-( trichloromethylthio) cyclohex-4-en-l ,2-

tlicarboximidc (CAPTAN) N-( l,l,2,2-tetrachloroethylthio)cyclohex-4-enl ,2-

dicarboximide (CAPTAFOL) N-methansulfonal-N-trichloromethylthiochloroaniline N -dichlorofluoromethylthio-N,N-dimethyl-N phenylsulfamide (DlCHLOFLUANlD) O-ethyl-S-benzyl-phenyldithiophosphate 0,0-diethyl-S-benzyl-thiolphosphate disodium-ethylene-l ,Z-bis-dithiocarbam ate (NABAM) zinc-ethylene-l ,Z-bis-dithiocarbamate (ZINEB) manganese-ethylene-l,Z-bis-dithiocarbamate (polymeric) (MANEB) tetramethylthiuramdisulfide (THIRAM) l-oxy-3-acetyl-6-methyl-cyclohexene-( 5 )dione-( 2,4)

DEBYPR ACET CAC 8-hydroxyquinoline (S-QUINOLINOL) Z-dimethylamino-6-methyl-5-n-butyl-4-hydroxypyrimidine methyl-N-benzimidazole-2-yl-N-( butylcarbamoyl carbamate (BENOMYL) 2-ethylamino-6-methyl-5n-butyl-4- hydroxypyrimidine 2,3-dicyano-l ,4-dithia-anthraquinone (DlTHlA- NON) 2-(4-thiazolyl)-benzimidazole 3,5-dimethyltetrahydro-l ,3,5-thiadiazine-2-thione (DAZOMET) 2,3-dihydro-5-carboxanilido-6-methyl-1,4-oxathine pentachlorobenzyl alcohol.

Furthermore, the compounds of the formula I are suitable for combating plant pathogenic nematodes,

The compounds of the formula I may be used as pure active substances or together with suitable carriers and- /or additives. Suitable carriers and additives can be solid or liquid and correspond to the substances conventionally used in formulation technique such, for example, as solvents dispersants, wetting agents, adhesives, thickeners, binders and/or fertilisers.

For application, the compounds of the formula I may be processed to dusts, emulsion concentrates, granules, dispersions, sprays, to solutions, or suspensions in the conventional formulation which is commonly employed in application technology. Mention may also be made of cattle dips and spray races", in which aqueous preparations are used.

Dusts agents according to the invention are manufactured in known manner by intimately mixing and/or grinding active substances of the formula I with the suitable carriers, optionally with the addition of dispersants or solvents which are inert towards the active substances. The active substances may take and be used in the following forms: Solid forms:

Dusts, tracking agents, granules, coated granules, im-

pregnated granules and homogeneous granules. Liquid forms:

a. active substances which are dispersible in water:

wettable powders, pasts, emulsions:

b. solutions.

To manufacture solid forms (dusts, tracking agents), the active substances are mixed with solid carriers. Suitable carriers are, for example: kaolin, talcum, bolus, loess; chalk, limestone, ground limestone, attaclay, dolomite, diatomaceous earth, precipitated silica, alkaline earth silicates, sodium and potassium aluminum silicates (feldspar and mica), calcium and magnesium sulphates, magnesium oxide, ground synthetic materials, fertilizers, for example ammonium sulphate, ammonium phosphate, ammonium nitrate, urea, ground vegetable products, such as corn meal, bark dust, sawdust, nutshell meal, cellulose powder, residue of plant extractions, activated charcoal etc. These substances can either be used alonepr in admixture with one another.

Granules can be very easily manufactured by dissolving an active substance of the formula I in an organic solvent and applying the resulting solution to a granulated material, for example attapulgite, SlO granicalcium, bentonite etc. and then evaporating the solvent.

Polymer granules can also be manufactured by mixing the active substances of the formula I with polymerisable compounds (urea/formaldehyde; dicyandiamide/formaldehyde, melamine/formaldehyde or others), whereupon a mild polymerisation is carried out that does not affect the active substances and in the process of which the granulation is carried out during the gel formation. It is more advantageous to impregnate finished, porous polymer granules (urea/formaldehyde, polyacrylonitrile, polyester or others) which have a specific surface area and a favourable predeterminable adsorption/desorption ratio, with the active substances, for example in the form of their solutions (in a low boiling solvent) and to remove the solvent. Polymer granules of this kind in the form of microgranules having a bulk density of 300 g/litre to 600 g/litre can also be manufactured with the aid of atomisers. The dusting can be carried out from aircraft over extensive areas of cultures of useful plants.

It is also possible to obtain granules by compacting the carrier with the active substance and carriers and subsequently comminuting the product.

To these mixtures can also be added additives which stabilize the active substance and/or non-ionic, anionic and cationic surface active substances, which, for example, improve the adhesion of the active ingredients on plants or parts of plants (adhesives and agglutinants) and/or ensure a better wettability (wetting agents) and dispersibility (dispersing agents). Examples of suitable adhesives are the following: olein/chalk mixture, cellulose derivatives (methyl cellulose, car boxymethyl cellulose), hydroxyethyl glycol ethers of monoalkyl and dialkyl phenols having to ethylene oxide radicals per molecule and 8 to 9 carbon atoms in the alkyl radical, lignin sulphonic acids, their alkali metal and alkaline earth metal salts, polyethylene glycol ethers (carbowaxes), fatty alcohol polyethylene glycol ethers having 5 to ethylene oxide radicals per molecule and 8 to 18 carbon atoms in the fatty alcohol moiety. condensation products of ethylene oxide/propylene oxide, polyvinyl pyrrolidones, polyvinyl alcohols. condensation products of urea and formaldehyde, and also latex products.

The water-dispersible concentrates of the active substance, i.e. wettable powders, pastes and emulsifiable concentrates, are agents which can be diluted with water to any concentration desired. They consist of active substance, carrier, optionally additives which stabilize the active substance, surface-active substance and anti-foam agents and, optionally, solvents.

Wettable powders and pastes are obtained by mixing and grinding the active substances with dispersing agents and pulverulent carriers in suitable apparatus until homogeneity is attained. Suitable carriers are, for example, those mentioned for the solid forms of application. ln some cases it is advantageous to use mixtures of different carriers. As dispersing agents there can be used. for example, condensation products of sulfonated naphthalene and sulfonated naphthalene derivatives with formaldehyde.condensation products of naphthalcnc or naphthalene sulfonic acids with phenol and formaldehyde, as well as alkali, ammonium and alkaline earth metal salts of lignin sulfonic acid, in addition, alkylaryl sulfonates, alkali and alkaline earth metal salts of dibutyl naphthalene sulfonic acid, fatty alcohol sulfates such as salts of sulfated hexadecanols, heptadecanols, octadecanols, and salts of sulfated fatty alcohol glycol ethers, the sodium salt of oleoyl ethionate, the sodium salt ofoleoyl methyl tauride, ditertiary acetylene glycols, dialkyl dilauryl ammonium chloride and fatty acid alkali and alkaline earth metal salts.

Suitable anti-foam agent are silicones.

strained with the additives cited hereinabove in such a manner that, in Wettable powders, the solid particle size of from 0.02 to 0.04 and in pastes. of 0.03 is not exceeded. To produce emulsifiable concentrates and pastes, dispersing agents such as those cited above, organic solvents and water are used. Examples of suitable solvents are: alcohols, benzene, xylene, toluene. dimethyl sulfoxide, and mineral oil fractions boiling between l20 and 350C. The solvents must be practically odourless, not phytotoxic, inert to the active substances.

Furthermore, the agents according to the invention can be applied in the form of solutions. For this purpose the active substance or several active substances of the general formula I dissolved in suitable organic solvents, mixtures of solvents or in water. Aliphatic and aromatic hydrocarbons, chlorinated derivatives thereof, alkyl naphthalenes, and mineral oils singly or in admixture with each other, can be used as organic solvents.

The content of active substances in the above described agents is between 0.1 to in which connection it should be mentioned that, in the case of application from aircraft or some other suitable means of application, it is possible to use concentrations of up to 99.5% or even pure active substance.

The active substances ofthe formula I can, for example, be formulated as follows:

Dust

The following substances are used to manufacture a) a 5% and b) a 2% dust:

a) 5 parts of active substance 95 parts of talcum b) 2 parts of active substance l part of highly disperse silica 97 parts of talcum.

The active substances are mixed with the carriers and ground. Granules The following substances are used to produce 5% granules:

5 parts of active substance. 0.25 parts of epichlorohydrin, 0.25 parts of cetyl polyglycol ether. 350 parts of polyethylene glycol. 91 parts of kaolin (particle size 0.3 0.8 mm).

a) 40 pans of active substance.

5 pans of sodium lignin sulphonate.

l pan of sodium dibutyl-naphthalene sulphonate.

54 parts of silica acid. b) 25 pans of active substance.

45 parts of calcium lignin sulphonate L9 parts of Champagne chalk/hydroxyethyl cellulose mixture (1:1).

5 pans of sodium dibutyl naphthalene sulphonate, .5 pans of silica acid.

5 pans of Champagne chalk.

l pans of kaolin.

3 pans of a mixture of the sodium salts of saturated fatty alcohol sulphates.

5 parts of naphthalenesulphonic acid/formaldehyde condensate,

parts of kaolin.

a) parts of active substance.

parts of epoxidised vegetable oil. parts of a combination emulsifier consisting of fatty alcohol polyglycol ether and alkylarylsulphonate calcium salt. parts of dimethylformamide. parts of xylene. parts of active substance. parts ol epoxitlised vegetable oil. parts of an alkylarylsulphonate/fatty alcoholpolyglycol ether mixture 5 parts of dimethylforntamide. 57.5 parts of xylene.

From these concentrates it is possible to produce, by dilution with water, emulsions of any desired concentration.

Spray:

The following constituents are used to prepare a 5% spray:

5 parts of active substance, 1 part of epichlorohydrin. 94 parts of benzine (boiling limits l60 190C).

EXAMPLE 1 Manufacture of the Starting Material a. 1-isopropyl-5-chloro-3-hydroxy-1,2,4-triazole 127 g of l-isopropyl-3-hydroxy-l ,2,4-triazole and 276 ml of tricthylamine are dissolved in 1200 ml of absolute alcohol. The solution turns cloudy yellow. While cooling (26 to 30C). 106.5 g of chlorine (dried by concentrated sulphuric acid) are passed in within 30 minutes. In the process. the yellow solution initially becomes clcar. Subsequently tricthylamine hydrochloride precipitates as crystalline product. which is filtered off after stirring for 1 further hour. The filtrate is concentrated to dryness in a rotary evaporator. The brown residue is dissolved in 1 litre of water and 1 litre of ether. The mixture is extracted and separated in a separating funnel. The aqueous phase is extracted 3 times with 500 ml of ether on each occasion. The combined ether phases are dried over sodium sulphate, the drying agent is filtered off and the filtrate is concentrated to dryness. The light brouwn residue is dissolved in 500 ml of carbon tetrachloride containing activated charcoal,

whereupon the mother liquor is concentrated to one third of its volume and then cooled. The active substance crystallises out and is dried in vacuo for 15 hours at 60C/l5 mm Hg. Yield: 96.3 g (60% of theory); m.p. l03lO5C. b. l-phenyl-5-chloro-3-hydroxy-l,2.4-triazolc 32.2 g of l-phenyl-3-hydroxy-l ,2,4-tria7.ole and 40.5 g of tricthylamine are dissolved in 300 ml of absolute alcohol. While cooling, 21.3 g of chlorine are passed in (20 to 30C). Triethylamine hydrochloride is filtered off and the filtrate is concentrated in a rotary evaporator. The residue is treated with 300 ml of water and extracted 4 times with 200 ml of ether each time. The combined ethereal extracts are dried over sodium sulphate. The drying agent is filtered off and the filtrate concentrated. The solid residue is recrystallised from ml of acetonitrile. Yield: ll.4 g (29.2% of theory); m.p. l47l49C. c. l-phenyl-5-chloro-3-hydroxy-l ,2,4-triazole 32.2 g of l-phenyl-3-hydroxy-l,2,4-triazole and 40.5 g of tricthylamine in 300 ml of dimethyl formamide. While cooling with ice, 21.3 g of chlorine gas are passed in at 20 to 30C. Subsequently the resulting trietylamine hydrochloride is filtered off and the solvent is distilled off in vacuo. The residue is taken up in 300 ml of water and extracted 4 times with 200 ml of ether. The combined ethereal extracts are dried over sodium sulphate and, after the solvent has been filtered off, concentrated in vacuo. The residue is recrystallised from acetonitrile. Yield: 15.0 g (38.4% of theory); m.p. l46l47C. d. l-ethyl-5-chloro-3-hydroxy-l,2,4-triazole 71.5 g of chlorine is passed into a solution of 75.5 g of l-ethyl-3-hydroxy-l,2,4-triazole and ml of triethylamine in 800 ml of absolute ethanol. the exothermic reaction is kept at 20 to 30C while cooling. Triethylamine hydrochloride is precipitated. The batch is further stirred for 2 hours after the chlorine has been passed in. Triethylamine hydrochloride is filtered off and the filtrate concentrated. The residue is dissolved in 500 ml of ether and 500 ml of water. The phases are separated and the aqueous phase is extracted 3 times with 300 ml of ether each time. The ethereal extracts are dried over sodium sulphate. The drying agent is filtered off and the filtate concentrated. The residue is recrystallised from a mixture of 400 ml of xylene and 250 ml of ligroin and dried in vacuo. Yield: 28.7 g (29% of theory); m.p. l08l l0C. c. l-isobutyl-5-chloro-3-hydroxy-l,2.4-triazolc 241 g of l-isobutylJ-hydroxy-l,2,4-triazolc and 475 ml oftriethylamine are dissolved in 2100 ml ofabsolutc ethanol, and 182 g of chlorine are passed in while cooling at 20-30c. The solution is stirred for H4 hours at room temperature, after which the tricthylamine hydrochloride is filtered off. The filtrate is concentrated in a rotary evaporator, the residue dissolved in 1000 ml of ether and 1000 ml of water are added. The phases are separated and the aqueous phase is extracted 3 times with 300 ml of ether each time. The ether phase is dried and concentrated. The residue is recrystallised from ligroin/xylene. Yield: 104.7 g (34% of theory); mp. 8486C.

The following compounds are manufactured in analogous manner:

m.p. 26-30C mp. 4 l-45C Continued l-sec.-butyl3-hydroxy-5chloro-l ,ZA-triazole 1-n-pentyl-3-hydroxy-5-chlorol .2.4-triazole l-sec.-pentyl-3-hydroxy-5ehloro-1.2,4-triazole l-n-hexyl-3-hydroxy-5-chloro-l,ZA-triazole H2, 2'. 2'-trimethy|-propyl'3-hydroxy-5-chloro-l.2.4-triazole eyclopentyl--chloro-1.2.4-triazole cyclophenyl-S-chloro-1,2,4-triazole l n-phenylethyl 3 hydroxy-5-chlor0-l .2.4-triazole Jdiplwnylmethyl1-3-hydroxy-5-chloru-l .2.4-triazole Z '-chlurophenyl J-Il-hydroxy-S-chloro- I ,2.4-triazole '-chlorophenyl J-3-hydroxy-5-chloro l .2.4-triazole 4 '-ch|oruphenyl )-3-hydroxy-5-chlorol .ZA-triazole (2'.5-dichlorophenyl)-5'hydroxy5-ch|oro-1.2,4-triazolc f. 1-isopropyl-5-bromo-3-hydroxy-l,2,4-triazole 63.9 g of l-isopropyl-l.2,4-triazolyl-(3)-benzoate with a melting point of 5557C (manufactured from 1-isopropyl-3-hydroxy-1 2,4-triazole and benzoyl chlo ride). 53.4 of N-bromo-succinamide and 0.2 g of azoisolmtyrontrile in 550 ml of carbon tetrachloride are heated together for 48 hours to reflux. After the reaction mixture has been cooled to 0C, the precipitate which has formed is filtered off with suction and heated to 75C in 600 ml of water. The undissolved portion is filtered off and dried in vacuo, to give 40 g of 1- isopropyl-S-bromo-l,2,4-triazolyl-(3)-benzoate in the form of crystals melting at 125-130C.

361 g of this intermediate product are treated with 1950 ml of Zn NaOH and the mixture is heated to 60C. The solution is cooled to C, filtered clear with activated charcoal over Hyflo, and the filtate is acidified with 390 ml of concentrated hydrochloric acid in 2000 ml of water. White crystals of 1-isopropyl-3-bromo-5- hydroxy-1,2,4-triazole (m.p. 155-l57C) are obtained.

g. 1Asopropyl-S-fluoro-3-hydroxy-l,2,4-triazole 16.2 g of 1-isopropyl-Schloro-3-hydroxy-1,2,4- triazole, 2) g of dry potassium fluoride and 150 ml of sulpholane are heated together for 16 hours to l6()-2(1UC. The solvent is evaporated off in a high vacuum and the residue then treated with 10% acetic acid and extracted with ethyl acetate. The ethyl acetate is evaporated off and the residueal solid is recrystallised from water. in the process of which l-isopropyl-S- fluoro-3-hydroxy-1 ,2,4-triazo1e is obtained in the form of white crystals with a melting point of 8095C. The product can be recrystallised from an organic solvent in order to purify it further.

Manufacture of the New Phosphorus Compounds a. 0,0-diethy1-O-[ 1-isopropyl-5-chloro-l,2,4-triazolyl- (3 ]-thio phosphate 22.5 g of 1-isopropyl-5-chloro-3-hydroxy-l,2,4- triazole and 19.3 g of potassium carbonate in 500 ml of Lp. 154- l 60C Lp. 128130( mp. l39l-llC m.p. 1 12-1 14C m.p. [SS-158C methyl ethyl ketone are heated for 2% hours to reflux and the mixture is then cooled to room temperature. In the course of 15 minutes 26.3 g of diethylthiophosphoric chloride are added dropwise and the solution is heated for 3 hours to reflux. it is cooled and the salts are filtered off with the aid of Hyflo and washed with methyl ethyl ketone. The clear filtrate is evaporated in vacuo. The residue is purified by chromatography over a short silica gel column with 2% methanol in chloroform as eluant. The solvent is afterwards distilled off and the compound of the formula Hu 1,4867 is obtained. b. 0,0-diethylO-l l-phenyl-S-chloro-l .2.4-triazolyl- (3)1-thiophosphate l 1.4 g of 1-phenyl-5-chloro-3-hydroxy-l ,2,4-triazole and 8.0 g of potassium carbonate in 250 ml of methyl ethyl ketone are heated for 2 hours under reflux and the mixture is subsequently cooled to room temperature, 10.8 g of diethylthiophosphoric chloride are added dropwise and the solution is heated again for 1 Va hours under reflux. It is then stirred overnight at room temperature. The salts are filtered off using Hyflo and the clear filtrate is evaporated in vacuo, to give the compound of the formula n 1,5449. c. O-ethy1-O-[ l-isopropyl-S-chloro-l ,2,4-triazolyl- (3)]-methylaminothiophosphoric acid ester 32.2 g of 1-isopropyl-5-chloro-3-hydroxy-1,2,4- triazole and 27.6 g of potassium carbonate were heated under reflux for 2 hours in 400 ml of methyl ethyl ketone. The resulting slurry was cooled to room temperature and 347 g of O-ethyl-S-methylaminodithiophosphoric chloride in 100 ml of methyl ethyl ketone were added dropwise. The batch was heated to reflux once more for 2 hours and subsequently stirred over night at room temperature. The salts were filtered off using Hyflo and the solvent distilled off from the filtrate in vacuo. The residue was purified by chromatography over a short silica gel column with chloroform as eluant, giving the compound of the formula S T- (CH CL N !N /OC H Cl"k O P NHCH 11 l,5l30. d. 0,0-dimethyl-O-[ l-isopropyl-S-chloro-l ,2.4-

e. 0,0-dimethyl-O-[ l-isopropyl-S-chloro-l ,2,4-tria2olyl-(3)]-phosphate 32.2 g of l-isopropyl-3-chloro-5'hydroxy-l2,4- triazole and 27.6 g of potassium carbonate are heated under reflux for 2 hours in 400 ml of methyl ethyl ketone and the mixture is subsequently cooled to room temperature. 28.9 g of dimethylphosphoric chloride in 100 ml of methyl ethyl ketone are added dropwise and the solution is heated again under reflux for 2 hours. The batch is then stirred overnight at room temperature. The salts are then filtered off using Hyflo and the filtrate is concentrated in vacuo. The oily, dark residue is purified by chromatography over a short silica gel column with chloroform/1% methanol, to give the compound of the formula Cl P The following compounds are also manufactured in analogous manner:

8 3 2 n ocn R -N-N z a-LV w- 2 N 2 0011 x P 3 N O- N lAW/O. R3

R1 R3 R2 Z Physical Data OC2H5 NHCH(CH3)2 c1 0 n 2O 1,5273 0 0 11 OC2H5 NH-CH(CH3)2 01 s Stnp.. 52 v H oc H -N(CH5)2 01 s n 2O 1,9019

v n OC2H5 1111011 Br s .i ao 1, 237 6 H -OC2H5 1m c1 6 n ao 1, 92

CH -cn 3 -oc n -NHCH5 01 s n 2O 1, 1 88 C H (tert) -C2H5 OC2H5 OC2H5 01 s n 'ao 1,5032 H -OC2H5 0c 11 (:1 s n 20 1,4871 C H -OC2H5 -OC2H5 01 s n ZO 1,4882 C2H5 --o0H oc1a (:1 s n ZO 1,4939

C4Hq ak') v 0611 #3011 01 s n 2O 1,4),3 a n -00 -0cn 01 s n 'aQ 1,4966 -OCH3 ocn 01 s 11 20 1,6666 1 AC. c 11 (,2H5 00 11 01 11 20 1,, ce O -Cntinued R 11 R X Z Physical Data C c @on OC H sc a 1 s n 2O 1,55JO

l CH- oc.,H oc tt 01 s l CH-- oca octt (:1 s

i ct1@ e a ec.,H 01 s OC H oc H 01 s oc a -NHCH 01 s 51-59 0 0 "CH. -,I "i m..:"-

3 7(1) OC NI- -CH(CH Cl 0 p 5) 6 C EXAMPLE 2 EXAMPLE 4 A. Insecticidal Ingest Poison Action 30 Action against Aulacopliera femora/is, Pachmoda and Tobacco and potato plants were sprayed with a Chortophila larvae 0.05% aqueous emulsion (obtained from a 10% emulsitiable concentrate).

After the coating had dried. the tobacco plants were populated with Egyptian cotton leafworms (Spoa'opu'ru Sterilized compost earth was homogeneously mixed with a wettable powder containing of active substance so that there resulted a rate of application of 8 kg of active substance per hectare. [mm-am) and the potato plants with Colorado potato Young wcchcm plums (cucumislwpm were put into b It! larva L m'n Mars 1 d 'ccmlim'um). The test was c irritd out -ti 4 ind (207:- rcl-ttive humidity in the plastic pots with thL treated (3 plants per d]- z t of t=7- .E;-h t Nt -m d d'- above test the compounds according to Example 1 dislzfy g t 5 23 33 247 z i' g i z P i L f 4 t fr spodoptcra lmor' 4t) Pachmoda or Chortophila larvae. The control was carg 'T Fe l ried out 4, 8, l6 and 32 days after depositing the larvae. z g fi z i i f gg rooted bean [ants At 80l00% kill afterthe first control,afresh infestas f zz ale? P into a 0 CW0 q activ: Sub tion with 5 larvae each was carried out in the same soil stance solution (obtained from a 10% emulsifiable con- M sample: with 3 new P i If h acimty Centrate) After 24 hours aphids F fabae) were less than 80%. the remaining larvae remained in the soil laced the arts of lam above the so The sample until the control immediately following If an :p were prstected from Bonnet and g actiion y active substance a rate ofapplication of 8 kg/ha still means of a special device The test was carried out at ett'ected a 100% kill. a further control with 4 and 2 kg 24C and 70% relative humidity. ln the above tests the so of Substance per hccwrc Came}! 1 I compounds according to Example I displayed good ini In move test Compounds According to sccticidul ingcst poison action and Systemic insecticidal ple l displayed action against Aulucop/zoru feHlUI'tI/IA', action Pachmoda and Chortophrla larvaev EXAMPLE 3 EXAMPLE 5 Action against Chilo suppressalis Action against Ticks Six rice plants at a time of the variety Caloro were A. Rhicep/zalus bursa transplanted into plastic pots (diameter at the top 17 Five adult ticks and 50 tick larvae were counted into cm) and reared to a hei ht of about cm. Infestation a lass tube and immersed for l to 2 minutes in 2 ml of g g with Chilo su ressalls larvae (L: 3-4 mm lon took 60 an a ueous emulsion from an emulsion series each con- PP 2 q lace 2 da s after the active substance had been a tainin 100, 10, l and ().l m of test substance. The P y P 2 PP plied in granule form to the paddy water (rate of applitube was then sealed with a standardized cotton wool cation: 8 kg of active substance per hectare). Evalua plug and placed on its head. so that the active subtion of the insecticidal action took place 10 days after stance emulsion could be adsorbed by the cotton wool. application of the granules. in the case of the adults evaulation took place after The compounds according to Example I were active in the above test against Chilo suppressalis.

2 weeks, and in that ofthe larvae after 2 days. Each test was repeated twice.

B. Boopliilus microplus (larvae) Tests were carried out in each case with OP- sensitive larvae using an analogous dilution series as in the case of test A. (The resistence refers to the tolerability of Diazinon). The compounds according to Example I acted in the above test against adults and larvae of Rliipic'eplmlus bursa and sensitive and OP rcsistent larvae of Boopliilus microplus.

EXAMPLE 6 Acaracidal action P/HLYUU/ILS' vulgaris (dwarf beans) have an infested piece of leaf from a mass culture of Tetranychus urticae placed on them 12 hours before the test for the acaricidal action, The mobile stages which have migrated are sprayed with the emulsified test preparations from a chromatography atomizer so that the spray broth does not run off. The nunber of living and dead larvae, adults and eggs are evaluated after 2 to 7 days under a stereoscopic microscope and the result expressed in percentages. During the interim, the treated plants are kept in greenhouse compartments at C.

The compounds according to Example I are active in the above test against eggs, larvae and adults of Telranychus urticae.

EXAMPLE 7 Action against soil Nematodes To test the action against soil nematodes, the active substance (in the concentration indicated in each case is applied to and intimately mixed with soil infected with root gall nematodes (Mefoidgyne avenaria). Immediately afterwards. tomato cuttings are planted in the thus prepared soil in a series of tests and after a waiting time of 8 days tomato seeds are sown in another test series.

In order to assess the nematocidal action, the galls resent on the roots are counted 28 days after planting and sowing respectively. The compounds according to Example 1 display good action against Mcloidgyne avenuriu.

What is claimed is:

l. A compound of the formula wherein X represents fluorine, chlorine or bromine; Z represents oxygen or sulphur; R represents C C alkyl, C -C cycloalkyl, or phenyl, benzyl, phenethyl, diphenylmethyl or optionally substituted by halogen. nitro. alkyl. halogenoalkyl, alkoxy, alkylsulphinyl or alkylsulphonyl. the alkyl groups of which each have 1-6 carbon atoms; R represents C C alkoxy. C C alkylthio. amino, monoor di(C,C,,,)alkylamino: and R represents C C alkyl, C C alkoxy, C ia2llk \'iIl1lU, phenyl, phenoxy, amino. monoor di(C C lalkylamino. 2. A compound according to claim 1, wherein X rep resents chlorine or bromine; Z represents oxygen or sulphur, R represents alkyl having 1 to 19 carbon atoms, cyclopentyl, phencthyl, diphenylmethyl or R represents mcthoxy, cthoxy or propoxy, R represents methyl, ethyl, mcthoxy, cthoxy, propylthio, amino, methylamino and dimethylaminov 4. A compound according to claim 3 of the formula 0,0-diethyl'O-[ l -ethyl-5-chloro-l ,2,4-triazolyl-( 3 )lthiophosphate.

5. A compound according to claim 3 of the formula O-ethyl-S-propyl-O-[ l-isopropyl-S-chloro-1,2,4- triazolyl-( 3 )l-dithiophosphate.

6. A compound according to claim 3 of the formula O-ethyl-S-propyl-O-[ l-benzyl5chloro-1,2,4-triazolyl- (3)]-dithiophosphate.

7. A compound according to claim 1 which is 0,0- diethyl-O-[ lisopropyl-5-chloro-l ,2,4-triazolyl-( 3 )lthiophosphatc. 

1. A COMPOUND OF THE FORMULA
 2. A compound according to claim 1, wherein X represents chlorine or bromine; Z represents oxygen or sulphur, R1 represents alkyl having 1 to 19 carbon atoms, cyclopentyl, phenethyl, diphenylmethyl or
 3. A compound according to claim 2, wherein X represents chlorine, Z represents sulphur, R1 represents alkyl, with 1 to 6 carbon atoms, cyclopentyl, phenyl, 3-trifluoromethylphenyl, benzyl, diphenylmethyl or
 4. A compound according to claim 3 of the formula O,O-diethyl-O-(1-ethyl-5-chloro-1,2,4-triazolyl-(3))-thiophosphate.
 5. A compound according to claim 3 of the formula O-ethyl-S-propyl-O-(1-isopropyl-5-chloro-1,2,4-triazolyl-(3)) -dithiophosphate.
 6. A compound according to claim 3 of the formula O-ethyl-S-propyl-O-(1-benzyl-5-chloro-1,2,4-triazolyl-(3))-dithiophosphate.
 7. A compound according to claim 1 which is O,O-diethyl-O-(1-isopropyl-5-chloro-1,2,4-triazolyl-(3))-thiophosphate. 